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WO2016162300A1 - Composition de caoutchouc de silicone - Google Patents

Composition de caoutchouc de silicone Download PDF

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Publication number
WO2016162300A1
WO2016162300A1 PCT/EP2016/057325 EP2016057325W WO2016162300A1 WO 2016162300 A1 WO2016162300 A1 WO 2016162300A1 EP 2016057325 W EP2016057325 W EP 2016057325W WO 2016162300 A1 WO2016162300 A1 WO 2016162300A1
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WIPO (PCT)
Prior art keywords
group
sulfur
component
inorganic filler
silicone rubber
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PCT/EP2016/057325
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English (en)
Inventor
Masato Kamiya
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Wacker Chemie AG
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Wacker Chemie AG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • C08K5/372—Sulfides, e.g. R-(S)x-R'
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/548—Silicon-containing compounds containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups

Definitions

  • the present invention relates to an addition-curable liquid silicone rubber composition capable of forming a cured product that is formed only by primary curing and has an excellent compression set property even after exposure to air over an extended period.
  • Silicone rubber has excellent heat resistance, cold resistance, electrical insulation, and weatherability, and good environmental safety. For this reason, the silicone rubber is widely used for various applications including automotive parts such as a connector seal and a spark plug boot, electrical and electronic parts such as a roller for a copying machine and a packing for a microwave oven,
  • liquid silicone rubber can be applied to automation by injection molding, mass production by molding for a short time, and molding unnecessary for post-processing of a molded product without formation of a burr. Therefore, in recent years, the demand of liquid silicone rubber has rapidly increased and in particular, the demand for application of automotive water-proof seal has increased. Further, a material in which the amount of low molecular weight cyclic siloxane in silicone rubber is decreased in advance and a secondary thermal curing process can be omitted has been increasingly required. However, when the secondary thermal curing process is omitted, there is a problem in which compression set as an important property of silicone rubber is not sufficient. This problem has become more serious. Therefore, silicone rubber having good compression set without the secondary thermal curing process has been required.
  • Patent Literature 1 describes a silicone rubber composition that has low compression set immediately after molding while excellent tear strength and shore A hardness are maintained by adding precipitated silica as a reinforcing filler and using a low compression set additive .
  • Patent Literature 2 describes a liquid silicone rubber composition used for injection molding that has high strength and low compression set by adding precipitated silica as a reinforcing filler and a certain amount of siloxane having an alkenyl group in a state of raw rubber.
  • Patent Literature 1 Japanese Patent Application Laid- Open No. 2002-114909
  • Patent Literature 2 Japanese Patent Application Laid- Open No. 2009-221295
  • Patent Literatures 1 and 2 the strength and good compression set of silicone cured product are achieved, but the documents do not specifically describe whether such a good compression set property is obtained over an extended period. Further, the documents do not specifically describe whether such a good compression set property is obtained only by primary curing. Therefore, a problem in which compression set obtained only by primary curing is not sufficient cannot be solved.
  • the present invention has been made in view of the circumstances, and an object of the present invention is to provide a composition capable of forming a cured product having an excellent compression set property even after exposure to air over an extended period. Another object of the present invention is to provide an addition-curable liquid silicone rubber composition capable of holding an excellent compression set property over an extended period without a secondary thermal curing process.
  • the present inventor has intensively studied, and as a result, has found that when a compound obtained by reacting a sulfur-containing compound with a filler or a filler surface- treated with a sulfur-containing compound is mixed in an addition-curable silicone rubber composition, the problem can be solved.
  • the present invention has been completed on the basis of the knowledges.
  • a silicone rubber composition of the present invention contains (A) 100 parts by mass of
  • polyorganopolysiloxane having at least two alkenyl groups to be bonded to silicon atoms in one molecule and a viscosity of 10 to 1,000,000 mPa-s at 25°C, (B) an
  • organohydrogenpolysiloxane having at least two hydrogen atoms to be bonded to silicon atoms in one molecule in an amount corresponding to a ratio of the number of silicon atom-bonded hydrogen atoms to the number of the alkenyl groups in the component (A) of 0.5 to 10.0, (C) 5 to 70 parts by mass of silica having a specific surface area measured by a BET method of 50 m 2 /g or more, (D) 0.001 to 5.0 parts by mass of a sulfur- containing inorganic filler including an inorganic filler mixture obtained by mixing a sulfur-containing compound with an inorganic filler, an inorganic filler reactant obtained by reacting a sulfur-containing compound with an inorganic filler, or an inorganic filler surface-treated with a sulfur- containing compound, and (E) a catalytic amount of an addition reaction catalyst.
  • the silicone rubber composition has a viscosity of 50,000 to 5,000,000 mPa ⁇ s at 25°C and
  • the sulfur-containing compound used as the component (D) is preferably a thiocyanato group-containing compound, and more preferably a thiocyanato group- containing alkoxysilane compound.
  • the silica (C) is preferably wet silica.
  • silicone rubber composition of the present invention when a compound obtained by reacting a sulfur- containing compound with a filler or a filler surface- treated with a sulfur-containing compound is mixed, a cured product having an excellent compression set property even after exposure to air over an extended period can be obtained. Even when a secondary thermal curing process is not performed, such an excellent compression set property can be held over an extended period.
  • the component (A) is a polyorganopolysiloxane having at least two alkenyl groups to be bonded to silicon atoms in one molecule and a viscosity of 10 to 1,000,000 mPa-s at 25°C.
  • the component (A) is liquid at room temperature (23°C ⁇ 15°C, hereinafter as the same) .
  • the number of the alkenyl groups to be bonded to silicon atoms in one molecule is preferably 2 to 50, and more preferably 2 to 20.
  • the number of carbon atoms in each alkenyl group is preferably 2 to 8 , more preferably 2 to 6 , and further preferably 2. Therefore, it is more preferable that the alkenyl groups be a vinyl group.
  • the component (A) usually has an average composition formula of the following formula (1) :
  • R 1 s are the same or different
  • the number of carbon atoms in R 1 is preferably 1 to 8.
  • a is preferably 1.8 to 2.5, and more preferably 1.95 to 2.05.
  • Examples of the unsubstituted monovalent hydrocarbon group among the monovalent hydrocarbon groups represented by R 1 may include an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a
  • neopentyl group a hexyl group, a cyclohexyl group, an octyl group, a nonyl group, and a decyl group, an aryl group such as a phenyl group, a tolyl group, a xylyl group, and a naphthyl group, an aralkyl group such as a benzyl group, a phenylethyl group, and a phenylpropyl group, and an alkenyl group such as a vinyl group, an allyl group, a propenyl group, an aryl group such as a phenyl group, a tolyl group, a xylyl group, and a naphthyl group, an aralkyl group such as a benzyl group, a phenylethyl group, and a phenylpropyl group, and an alkenyl group such as a
  • substituted monovalent hydrocarbon group may include a group in which a part or all of the hydrogen atoms of the above-described unsubstituted monovalent
  • hydrocarbon group is substituted with a halogen atom such as a fluorine atom, a bromine atom, and a chloride atom, a cyano group, and the like.
  • a halogen atom such as a fluorine atom, a bromine atom, and a chloride atom, a cyano group, and the like.
  • Specific examples thereof may include a chloromethyl group, a chloropropyl group, a bromoethyl group, a trifluoropropyl group, and a cyanoethyl group. It is
  • the monovalent hydrocarbon group represented by R 1 be a methyl group, and it is more preferable that the monovalent hydrocarbon group represented by R 1 except for an alkenyl group be all a methyl group.
  • the component (A) may be one kind or a mixture of two or more kinds.
  • the content of alkenyl groups in the component (A) is usually 1.0 x 10 ⁇ 6 to 5.0 x 10 "4 mol/g, and preferably 1.0 x 10 ⁇ 5 to 2.0 x 10 ⁇ 4 mol/g.
  • the content of alkenyl groups is less than the above-described range, the rubber hardness is too low, and the resulting composition may be gel.
  • the content of alkenyl groups is more than the range, the
  • the alkenyl groups may be bonded to a silicon atom at the terminal, at the middle, or at the terminal and middle of the molecular chain. In order to impart an excellent mechanical property to a cured composition, it is preferable that the alkenyl groups be positioned at least at the terminal of the molecular chain.
  • the component (A) basically has a linear structure in which both terminals of the molecular chain are capped with a triorganosiloxy group and the main chain includes a repeating unit of diorganosiloxane .
  • the component (A) may have a
  • partially branched structure or a cyclic structure means 33% by mass or less of the component (A) .
  • the viscosity at 25°C of the component (A) is preferably 10 to 500,000 mPa ⁇ s, and more preferably 100 to 250,000 mPa-s.
  • the viscosity of the component (A) is 100 to 250,000 mPa-s, high fluidity is imparted to the silicone rubber composition before curing, and an excellent mechanical property is
  • the component (B) is an organohydrogenpolysiloxane having at least two hydrogen atoms to be bonded to silicon atoms in one molecule.
  • the component (B) is a component for curing the composition of the present invention into a rubber elastic body or a gel by reacting the hydrogen atoms to be bonded to silicon atoms in the component (B) with the alkenyl groups in the component (A) .
  • the component (B) is an organohydrogenpolysiloxane having at least 2, preferably 3 or more, more preferably 3 to 200, further preferably 3 to 100, or particularly preferably 4 to 50 hydrogen atoms (SiH groups) to be bonded to silicon atoms in one molecule.
  • the component (B) is one kind of
  • the component (B) acts as a curing agent for cross- linking and curing the composition by hydrosilylation reaction of the SiH groups in the molecule with alkenyl groups bonded to silicon atoms in the component (B) and the component (A) .
  • the component (B) usually has an average composition formula of the following formula (2) :
  • R 3 s are the same or different
  • R 3 in the formula (2) have 1 to 8 carbon atoms, c be 0.8 to 2.0 , d be 0.001 to 1.0, and (c + d) be 1.0 to 2.5. [0022]
  • R 3 may include the same groups as those exemplified in R 1 in the formula (1) . It is preferable that R 3 be a monovalent hydrocarbon group having no aliphatic
  • the component (B) may have any molecular structure such as linear, cyclic, branched, and three-dimensional network.
  • the number (or polymerization degree) of silicon atoms in one molecule is usually 2 to 300, preferably 3 to 200, and more preferably 4 to 150.
  • the viscosity of the silicone composition falls within a range suitable for injection molding. Therefore, this range is preferred.
  • the hydrogen atoms to be bonded to silicon atoms may be positioned at the terminal, at the middle, or at the terminal and middle of the molecular chain.
  • component (B) may include 1,1,3,3- tetramethyldisiloxane , 1,3,5, 7-tetramethylcyclotetrasiloxane, a methylhydrogensiloxane cyclic polymer, a
  • dimethylpolysiloxane having both molecular terminals capped with dimethylhydrogensiloxy groups
  • a dimethylsiloxane- methylhydrogen iloxane copolymer having both molecular
  • methylhydrogensiloxane-methylphenylsiloxane copolymer having both molecular terminals capped with trimethylsiloxy groups
  • a methylhydrogensiloxane-methylpheny1siloxane-dimethylsiloxane 2016/057325 copolymer having both molecular terminals capped with
  • the component (B) be a polymethylhydrogensiloxane containing a (CH 3 )HSi0 2 2 unit, a polymethylhydrogensiloxane containing a (CH 3 ) 2 Si0 2/2 unit, or a polymethylphenylhydrogensiloxane containing a (CH 3 ) (C e H 5 )Si0 2/2 unit .
  • the amount of the component (B) to be mixed is usually 0.2 to 20 parts by mass, and preferably 0.5 to 10 parts by mass, relative to 100 parts by mass of the component (A) .
  • the ratio of the number of silicon atom-bonded hydrogen atoms (SiH groups) in the present invention is the ratio of the number of silicon atom-bonded hydrogen atoms (SiH groups) in the present invention.
  • component (B) to the number of alkenyl groups in the component (A) is 0.5 to 10.0, and particularly preferably 0.8 to 5.0.
  • this ratio is less than the above-described range, cross- linking is insufficient, and a sticky rubber may be obtained.
  • this ratio is more than the range, bubbling appears in a molded product, and the molded product is difficult to be separated from a mold. The physical properties, particularly heat resistance after curing may be largely changed.
  • the silica of the component (C) imparts sufficient
  • silica of the component (C) for example, fumed silica (dry silica) or wet silica is used. In particular, wet silica is preferred since it has an excellent compression set property.
  • the silica of the component (C) has a specific surface area measured by a BET method of 50 m 2 /g or more, preferably 100 to 500 m 2 /g, and more preferably 150 to 300 m 2 /g. When the specific surface area of the component (C) is less than 50 m 2 /g, sufficient strength may not be achieved.
  • silica of the component (C) may be used as EP2016/057325 it is, it is preferable to use silica that is treated in advance with a hydrophobizing surface treatment agent, or silica that is surface-treated by addition of surface
  • the surface treatment agent a known surface treatment agent such as alkylalkoxysilane , alkylchlorosilane , alkylsilazane , a silane-coupling agent, a titanate-based treatment agent, and a fatty acid ester is used.
  • a known surface treatment agent such as alkylalkoxysilane , alkylchlorosilane , alkylsilazane , a silane-coupling agent, a titanate-based treatment agent, and a fatty acid ester is used.
  • One kind of the surface treatment agent may be used alone or two or more kinds thereof may be used simultaneously or separately.
  • the amount of the component (C) to be mixed is 5 to 70 parts by mass, and preferably 15 to 50 parts by mass, relative to 100 parts by mass of the component (A) .
  • the amount is less than 5 parts by mass, sufficient rubber strength may not be achieved.
  • compression set may be increased.
  • the silica of the component (C) be wet silica since the wet silica has an excellent compression set property.
  • the component (D) is a sulfur-containing inorganic filler including an inorganic filler mixture obtained by mixing a sulfur-containing compound with an inorganic filler, an inorganic filler reactant obtained by reacting a sulfur- containing compound with an inorganic filler, or an inorganic filler surface-treated with a sulfur-containing compound.
  • component (D) contains a sulfur- containing compound or is a reactant of sulfur-containing compound will be described below.
  • the composition contains a component having an action that does not affect a cross- linking reaction during primary curing and suppresses a cross- linking reaction in secondary curing or in heat history after the curing, the object is achieved.
  • the sulfur-containing compound has this action.
  • the sulfur-containing compound used for preparation of the component (D) is not limited to particular kinds, but it may be a generally used compound. Examples thereof may include an organic sulfur compound such as thiol (mercaptan,
  • bisthiocarbamoyl disulfane, and bisthiocarbamoyl polysufane) a thiuronium salt, thiocarbamate , dithiocarbamate , and Zn salt, Fe salt, Ni salt, Co salt, and Cu salt thereof, thiocyanate, and isothiocyanate ; a thiocarbonyl compound such as
  • thioaldehyde thioketone, thiolactone, and thiocarboxylic acid
  • a thiaheterocyclic compound such as thiophene, 1,2- dithiol, 1,3-dithiol, 1, 2-dithiol-thione, 1 , 3 -dithiol-thione , thiazole, mercaptothiazole , mercaptothiadizole , benzo-dithiol , benzo-dithiol-thione, benzothiazole , mercaptobenzothiazole , phenothiazole , and thanthrene .
  • a thiol group- containing compound (mercapto group-containing compound) and a thiocyanato group-containing compound are preferred, and a thiocyanato group-containing alkoxysilane compound is more preferred since availability is good and the compression set property is improved.
  • the component (D) have an action that does not suppress an addition reaction during primary curing and suppresses the reaction in subsequent heat history. It is not preferable that the component (D) be present in such a state that the component is likely to be released in the silicone rubber composition. In order to activate a releasing or suppression effect only at a point when the subsequent heat history is imparted, it is considered that the component (D) is mixed or reacted with the inorganic filler, or the
  • inorganic filler is present in the silicone rubber composition in a state of inorganic filler surface-treated with the
  • the sulfur- containing compound be chemically bonded to the surface of the inorganic filler or bonded to the surface of the inorganic filler by a chemical bond like a hydrogen bond.
  • inorganic filler is often covered with a polar chemical group, particularly a hydroxyl group.
  • a polar chemical group particularly a hydroxyl group.
  • the sulfur-containing compound has a chemical structure having a function of the bond.
  • the chemical bond is not limited, and preferably has an alkoxysilyl group. It is the most preferable that the sulfur- containing compound used as the component (D) be a sulfur- containing alkoxysilane .
  • the structure and molecular weight of sulfur-containing alkoxy compound that is preferably used as the component (D) and the kind and induction amount of the alkoxy group are not limited. Examples thereof may include a sulfur-containing alkoxysilane including mercaptoalkyl-alkyl-alkoxysilane having an average composition formula of the following formula (4), bis (trialkoxysilyl-alkyl) mono- , di-, and polysulfane having an average composition formula of the following formula (5) , and thiocyanatoalkyl trialkoxysilane having an average composition formula of the following formula (6) :
  • R 5 is a substituted or unsbustituted aliphatic saturated monovalent hydrocarbon group having 1 to 10 carbon atoms, and 6 057325 preferably 1 to 6 carbon atoms.
  • R 5 for example, an alkyl group is used.
  • a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, or a cycloalkyl group is
  • a cyclopentyl group, a cyclohexyl group, or a cycloheptyl group is more preferably used.
  • R 5 is a substituted or unsbustituted aliphatic saturated monovalent hydrocarbon group having 1 to 10 carbon atoms, and preferably 1 to 6 carbon atoms.
  • R 6 for example, an alkyl group is used, A methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cycloalkyl group, a
  • cyclopentyl group a cyclohexyl group, a cycloheptyl group, an aryl group, an alkaryl group, a phenyl group, a tolyl group, a xylyl group, a mesityl group, or a benzyl group is preferably used .
  • R 7 for example, a substituted or unsbustituted aliphatic saturated divalent hydrocarbon group having 1 to 10 carbon atoms, and preferably 1 to 6 carbon atoms is used.
  • R 7 is an alkylene group, preferably a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, or a phenylene group, and more preferably a propylene group .
  • R 8 and R 10 are the same as the groups of R 5 .
  • R 9 and R 11 are the same as the groups of R 7 .
  • n is 0 to 3, and preferably 0.5 to 2.5.
  • n is 1 to 10, and preferably 2 or 4.
  • the component (D) may be each of the sulfur-containing alkoxysilanes , a mixture of a mixture of the sulfur-containing alkoxysilanes with the inorganic filler, or a compound in which an inorganic filler is surface-treated with each of the sulfur-containing alkoxysilanes. It is more preferable that the sulfur-containing alkoxysilane be thiocyanatoalkyl
  • Examples of the inorganic filler that is mixed or reacted with the sulfur-containing compound or surface-treated with the sulfur-containing alkoxysilane may include silicon- containing fillers including silicon dioxide such as dry
  • silica and wet silica quartz powder, diatomaceous earth, calcium silicate, zirconium silicate, and zeolite, metal oxide such as iron oxide, zinc oxide, titanium dioxide, and aluminum oxide, and metal carbonate such as calcium carbonate,
  • magnesium carbonate, and zinc carbonate are magnesium carbonate, and zinc carbonate.
  • silicon dioxide is preferably used, and wet silica is more preferably used.
  • the amount of the component (D) to be mixed is 0.001 to 5.0 parts by mass, and preferably 0.01 to 2.0 parts by mass, relative to 100 parts by mass of the component (A) .
  • the addition reaction catalyst of the component (E) is a hydrosilylation reaction catalyst.
  • hydrosilylation reaction catalyst may include a platinum
  • catalyst such as platinum black, platinic chloride
  • chloroplatinic acid a reactant of chloroplatinic acid with monohydric alcohol, a complex composed of chloroplatinic acid and olefin, and platinum bisacetoacetate , a palladium catalyst, and a rhodium catalyst.
  • platinum and a platinum-based compound are examples of platinum and a platinum-based compound.
  • the amount of the addition reaction catalyst to be mixed can be a so-called catalytic amount.
  • the amount is usually 0.1 to 1,000 ppm, and particularly about 1 to about 500 ppm in terms of mass of platinum group metal relative to the total amount of the components (A) and (B) .
  • a filler such as quartz powder, diatomaceous earth, calcium carbonate, and aluminum oxide, a conductive filler such as carbon black, conductive zinc oxide, and metal powder, a hydrosilylation reaction controlling agent such as a nitrogen- containing compound, an acetylene compound, a phosphorus compound, a nitrile compound, carboxylate, a tin compound, a mercury compound, and a sulfur compound, a heat-resistant agent such as iron oxide, titanium oxide, and cerium oxide, an internal mold release agent such as dimethyl silicone oil, alkoxysilane that serves as an adhesiveness - imparting agent, thixotropic property- imparting agent, or an adhesion improver, a phenyl- modified silicone oil for imparting self-lubricating property to a cured silicone rubber, or the like, may be added.
  • a hydrosilylation reaction controlling agent such as a nitrogen- containing compound, an acetylene compound, a phosphorus compound, a nitrile compound,
  • the addition curable silicone rubber composition of the present invention can be obtained by uniformly mixing the components (A) to (E) and the optional component (s) at normal temperature. Further, the composition can be obtained
  • a conventional method can be adopted.
  • a liquid injection molding method is suitably adopted.
  • a curing condition primary curing
  • a heating condition including at 100 to 200°C for 5 seconds to 30 minutes, and preferably at 120 to 200°C for about 10 seconds to about 15 minutes may be adopted.
  • post curing can be performed under a condition including at 150 to 220°C, and particularly at 180 to 200°C, for about 0.5 to about 12 hours, and particularly for about 1 to about 6 hours.
  • the silicone rubber composition of the present invention has a viscosity of 50,000 to 5,000,000 mPa ⁇ s at 25°C and a shear rate of 0.9 s "1 .
  • part(s) represents part(s) by mass.
  • the base compound was cooled to normal temperature. To 100 parts of the base compound, 2.5 parts of
  • polymethylhydrogensiloxane having a (CH 3 )HSi0 2 / 2 unit and a (CH 3 ) 2 Si02 2 unit at a ratio of 33/67 and a viscosity of 150 mPa'S at 25°C (component (B) ) , 0.2 parts of silica filler surface-treated with thiocyanatopropyltriethoxysilane
  • component (E) 0.1 parts of acetylene alcohol as an additive for controlling a curing rate were each added, and the mixture was uniformly mixed, to prepare a silicone rubber composition according to the present invention .
  • the silicone rubber composition was press-cured at 170°C for 5 minutes to obtain a silicone rubber cured product.
  • the base compound was cooled to normal temperature. To 100 parts of the base compound, 2.5 parts of
  • polymethylhydrogensiloxane having a (CH 3 )HSi0 2 /2 unit and a (CH 3 ) 2 Si0 2 / 2 unit at a ratio of 33/67 and a viscosity of 150 mPa ⁇ s at 25°C (component (B) ) , 0.2 parts of silica filler surface-treated with thiocyanatopropyltriethoxysilane
  • component (E) 0.1 parts of acetylene alcohol as an additive for controlling a curing rate were each added, and the mixture was uniformly mixed, to prepare a silicone rubber composition according to the present invention .
  • the silicone rubber composition was press-cured at 170°C for 5 minutes to obtain a silicone rubber cured product.
  • a silicone rubber composition was prepared in the same manner as in Example 1 except that the silica filler surface- treated with thiocyanatopropyltriethoxysilane (component (D) ) was not added.
  • the silicone rubber composition was press-cured at 170°C for 5 minutes to obtain a silicone rubber cured product.
  • the hardness and compression set of the cured product were measured in accordance with JIS K 6249. The results are shown in Table 1.
  • a silicone rubber composition was prepared in the same manner as in Example 1 except that the silica filler surface- treated with thiocyanatopropyltriethoxysilane (component (D) ) was not added in Example 2.
  • the silicone rubber composition was press-cured at 170°C for 5 minutes to obtain a silicone rubber cured product.
  • the hardness and compression set of the cured product were measured in accordance with JIS K 6249. The results are shown in Table 1.
  • the addition-curable liquid silicone rubber composition of the present invention forms a cured product having the excellent compression set property even after exposure to air over an extended period. Even when a secondary thermal curing process is not performed, the excellent compression set property can be held over an extended period.
  • the composition is a material suitable for seal parts requiring heat
  • automotive seal parts such as an automotive connector waterproof seal part
  • seal parts for electrical and electronic apparatus including, for example, automotive seal parts such as an automotive connector waterproof seal part, and seal parts for electrical and electronic apparatus .

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une composition permettant de former un produit durci ayant une excellente propriété de déformation rémanente à la compression même après exposition à l'air sur une longue période. La composition contient (A) un polyorganopolysiloxane possédant au moins deux groupes alcényle devant être liés à des atomes de silicium dans une molécule et une viscosité allant de 10 à 1 000 000 mPa⋅s à 25 °C, (B) un organohydrogénopolysiloxane ayant au moins deux atomes d'hydrogène devant être liés à des atomes de silicium dans une molécule, (C) de la silice ayant une surface spécifique BET supérieure ou égale à 50 m2/g, (D) une charge inorganique contenant du soufre comprenant un mélange de charges inorganique obtenu par mélange d'un composé contenant du soufre avec une charge inorganique, un réactif de charge inorganique obtenu en faisant réagir un composé contenant du soufre avec une charge inorganique, ou analogue, et (E) un catalyseur de réaction d'addition, et la composition présente une viscosité allant de 50 000 à 5 000 000 mPa⋅s et une vitesse de cisaillement de 0,9 s-1.
PCT/EP2016/057325 2015-04-06 2016-04-04 Composition de caoutchouc de silicone Ceased WO2016162300A1 (fr)

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US5977249A (en) * 1996-08-29 1999-11-02 Wacker-Chemie Gmbh Liquid silicone rubber with improved compression set
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JP2002114909A (ja) 2000-08-11 2002-04-16 General Electric Co <Ge> 高引裂強さ、低圧縮歪の熱硬化性シリコーンエラストマー及び添加剤
JP2009221295A (ja) 2008-03-14 2009-10-01 Shin Etsu Chem Co Ltd 付加硬化性シリコーンゴム組成物及びシリコーンゴム硬化物

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US5569688A (en) * 1993-10-21 1996-10-29 Shin-Etsu Chemical Co., Ltd. Heat-curable silicone rubber compositions
US5977249A (en) * 1996-08-29 1999-11-02 Wacker-Chemie Gmbh Liquid silicone rubber with improved compression set
US5998548A (en) * 1997-08-18 1999-12-07 Wacker-Chemie Gmbh Compressible, sulfur-containing silicone rubber
JP2002114909A (ja) 2000-08-11 2002-04-16 General Electric Co <Ge> 高引裂強さ、低圧縮歪の熱硬化性シリコーンエラストマー及び添加剤
JP2009221295A (ja) 2008-03-14 2009-10-01 Shin Etsu Chem Co Ltd 付加硬化性シリコーンゴム組成物及びシリコーンゴム硬化物

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107418215A (zh) * 2017-08-15 2017-12-01 合肥卓立雅工程材料科技有限公司 机械强度高防水密封性好的橡胶止水带及其制备方法

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